Process of making phosphorus.



2'04. CHEMISTRY, Elf- HIUAL & WAVE ENERGY. BAFTSM 'No. 755,316. w PATENTED JULY 7,1903.

R. K. DUNCAN.

PROCESS OF MAKING PHOSPHORUS. nrmoumn mum no. 9. 1902.

B0 MODEL.

VENTOR Atlamey in: noun: PLIIIM no. mum-um! wummou. D. c

No. "reams.

ROBERT KENNEDY DUNCAN, OF

iatented July 7, 1903.

PATENT WASHINGTON, PENNSYLVANIA, ASSIGNOR TO GENERAL CHEMICAL COMPANY, OF N EWV YORK, N. Y.

PROCESS OF MAK ING. PHOSPHORUS.

srnormoarlon forming part of Letters Patent No. 733,316, dated July '7, 1903.

Application filed December 9,1902."

To all whom it may concern;

' Be it known thatI, ROBERT KENNEDY DUN- CAN, a resident of Washington, in the county of Washington and State of Pennsylvania,

have invented certain new and useful Im- 'pr0vemen ts;inProcesses for the Production of Phosphorus and I dohereby declare the following to be a full, clear, and exact description of the invention, such as will enable oth- 1o ers skilled in the art .to which it appertains mercial scale evaporated down and heated, under which. circumstances it became calcium metaphos-.

phate. This metaphosphate was then mixed with carbon and preferably sand and the phosphorus distilled out of the mixture. The phosphorus so produced was yellow phosphorus only and required purifying because of presence in it of carbonaceous and other impurities mechanically car riedover in the process of distillation. The methods of purifying were tedious,dangerous, and expensive,

o owing to the inflammable and poisonous nature of the yellow phosphorus. V

The above method has within recent years been largely displaced by what is known as the electric-furnace method of production,

which consists in the foli owing steps: Phosphatic material is mixe, with the necessary amount of carbonaceous material, and .the mixture is,placed in an electric furnace, un-

- der the intense temperature of which the 40 phosphorus is distilled out in the yellow form and is collected under water in the usual way.

The disadvantages of this process are- First. Only about sixty per cent. of the phosphorus contained in the charge can be 5 distilled out.

Second. It requires the very highest heat obtainable of an electric furnace to efifect such direct distillation, resulting in the consumption of a large amount of energy with 5o its attendant expense.

Serial No. 134,517.,(110 specimens.)

Third. Yellow phosphorus alone can be produced by this -method. In the event it is desired to producered phosphorus, which is a of the foregoing processes to heat the yellow .phosphorus so produced in closed tubes, under which circumstances it becomes slowly converted into red phosphorus.

Fourth. The yellow phosphorus produced by the method last described must be purified, as in the earlier process.

The object of my improved process is to produce pure red or yellow phosphorus more economically than has been possible by any process that has been heretofore employed; and with this end in view my invention consists, first, in the method of producing phosphorus consisting in subjecting phosphatic material to the decomposing action of an electric current and exposing the product derived therefromto the action of water and finally disassociating the crude gases evolved and producing either red or yellow phosphorus.

The invention further consists in certain other steps in the process, which will be hereinafter described, and pointed out in the claims. I 1

The accompanying drawing .is a diagrammatic illustration of an apparatus which may be employed for carrying my improved .,process into elfect.

Phosphatic material of any nature is used that will when heated with carbon result in a product from which phosphorus hydrids may be obtained-as,for instance,bone-black, bone-ash, or mineral phosphate. I have obtained good results from the use of bone-black and bone-ash. The phosphatic material is powdered and mixed with powdered carbon in approximately the proportions of seventyseven (77) parts of phosphatic material to twenty-three (23) parts of carbon, although these proportions may be varied. A small amount of tar is then preferably added to the mixture and serves as a binder to make -it cohere. The mixture is then dried and charged into an electric furnace A, which may be r any suitable type or construction, and heated by either a continuous, alternating, or intermittent current, which passes very valuable product, it is necessary in either lEMlSTRY, ELECTRICAL WAVE ENERGY.

hrough the electrodes and the mixture as it ;gradually fed between the adjacent ends f the electrodes, or the mixture may be therwise subjected to the heating or decomosing action of an electric current. A preminary heating of the mixture is effected y a hydrogemburner b, the hydrogen suplied thereto being a byproduct of the procss. The electric current supplied to the urnace is regulated so as not to produce a amperature sufiiciently high to break down we phosphid as it is produced into phoshorus and carbid. By employing the hydroen-burner to preliminarily heat the mixture reat economy in the use of electric energy is lfected, owing to the fact that a smaller volme of current will suifice to reduce the heat- 3 mixture to calcium phosphids than would e the case if the charge were not heated y the hydrogen-burner, and a much smaller olume of current will sufiice to produce the hosphids, which contain practically all the hosphorus in the original charge, than was :quired to produce phosphorus direct from )8 charge, which process, as has been stated, ields only about sixty per cent. of the phoshorus contained in the charge. The calum phosphid is continuously produced and removed from the furnace from time to me and discharged into any suitable recep- .cle B. In exposing phosphatic material to l9 action of an electric furnace various calum phosphids are produced, which may try according to the temperatures employed. he phosphids thus produced are then larged into either one of the decompositionlambers C O for the production of phosiorus hydrids in the following manner: D is a Water-tank, from which water is supied to the chambers O C by the pipes 01, hich are provided with suitable valves for ltting oif or controlling the supply of water the chambers, two being employed in ori! that while one is in use the other maybe eaned and charged and put in readiness for e. After one of the chambers has been arged with calcium phosphid and before tter has been admitted thereto hydrogen s is permitted to flow from the gasometer to such charged chamber and drive out and place the air contained, therein in order to oid the risk of explosion which would atnd the mixing of phosphorus hydrids with mospheric air. After the charge of calim phosphids has been thus covered and otected by hydrogen water is supplied to e chamber, with the result that a complex xture of phosphorus hydrids is evolved, rich is conducted from the chamber into a someter E, which serves as a pressure- ;ulator and which under some conditions ght be dispensed with. The phosphorus drids thus produced are passed through a ring-chamber F, which is filled with calcitphosphid,whi ch absorbs the water or mois- 'e contained in the phosphorus hydrids and o enriches the latter,- which are then conducted into a heater consisting of a jacket 'K, provided with a metal lining H and a is furnished with any desired number of jets, a supply of hydrogen from a gasometer being furnished thereto. By regulating the heat supplied to the heater either red or yellow phosphorus may be produced, a lesser amount of heat being required to produce red phosphorus. \Vhen red phosphorus is produced, it is formed in the tube and may be removed therefrom from time to time. If .yellow phosphorus is desired, a higher degree of heat is employed, with the result that the yellow phosphorus distils over and is collected under water in a suitable receptacle'- such, for instance, asin the lower part of a hydrogen-gasometer N--into which the resulting hydrogen is conducted and stored for use. The yellow phosphorus may be discharged through the valve 'm and collected in any suitable vessel on. The hydrogen may be used to preliminarily heat the charge in the electric furnace; also, to decompose the phosphorus hydrids, and, further, to replace the air in the decomposing-chambers. When it is desired to produce red phosphorus only, which is a product of great commercial value, the phosphorus hydrids are conducted into any suitable receptacle and subjected to the reducing action of an electric spark, which has the effect of breaking down the phosphorus hydrids and producing red phosphorus and hydrogen.

From the foregoing it will be observed that in exposing phosphatic material to the heat of an electric furnace various calcium phos' phids are produced, which may vary according to the temperature employed, and it is obvious that in the decomposition of these phosphids with water various phosphorus hydrids are evolved and that by my processthis complex mixture of -phorphorus hydrids is dissociated by the action of heat or other fication.

I do not restrict myself to the employment of the construction of apparatus herein shown and described for carrying my process into efiect, as other forms and constrnctions'of apparatus may be employed.

Having fully described my process, what I claim as new, and desire to secure by Letters Patent, is

1. The process of producing phosphorus, which consists in subjecting phosphatic material to the decomposing action of an electric current and producing phosphids, and subjecting said phosphids to the action of water and producing phosphorus hydrids, and finally dissociating the latter by the action of heat, substantially as set' forth.

2. The process of producing phosphorus, which consists in subjecting phosphatic material to the decomposing action of an electric current and producing phosphids, and subjecting said phosphids to the action of waelectric spark without the necessity of puri- Search burner L,located below the tube. The burner ro tion of water and producing phosphorus hydrids, and finally dissociating the latter by the action of heat, substantially as set forth. 4. The process of producing phosphorus,

.. which consists in subjecting phosphatic ma- 1 5 terial to the decomposing action of an electric current and producing phosphids, charging the said phosphids into a decomposing-chamber, admitting hydrogen to the chamber to expel the air therefrom, subjecting the phos- 2o phids to the action of water in said chamber and producing phosphorus hydrids, and finally dissociating the latter by the action of heat, substantially as set forth.

5. The process of producing phosphorus,

which consists in subjecting phosphatic material to the decomposing action of an electric current and producing phosphids, subjecting said phosphids to the action of water and producing phosphorus hydride, drying the latter, and then dissociating the mixture by electric sparking, substantially as set forth.

6. In a proeessfor producing phosphorus, dissociating gaseous hydrogen phosphids containing or associated with liquid and solid phosphids by the action of heat and producing phosphorus, substantially as set forth.

7. In a process for producing phosphorus, dissociating gaseous hydrogen phosphids containing or associated with liquid and solid phosphid by electric sparking and producing phosphorus, substantially as set forth.

In testimony whereof I have signed this specification in the presence of two subscribing witnesses.

ROBERT KENNEDY DUNCAN.

Witnesses: A. W. BRIGHT,

E. N. WATERS. 

